TWI664226B - Epoxy resin composition, resin sheet, prepreg and metal-clad laminated board, printed wiring board, semiconductor device - Google Patents

Abstract

An object of the present invention is to provide an epoxy resin composition, a resin sheet using the same, a metal-clad laminate, a printed wiring board, and a semiconductor device. The cured product of the epoxy resin composition has high heat resistance and water absorption, The dielectric constant is low. The epoxy resin composition of the present invention contains an epoxy resin and an amine-based hardener represented by the following general formula (1) as essential components.

(In the formula, the ratio of (a) (b) is (a) / (b) = 1 ~ 3; G is epoxy group; n is the repeating number, 0 ~ 5)

Description

Epoxy resin composition, resin sheet, prepreg and metal-clad laminated board, printed wiring board, semiconductor device

The present invention relates to an epoxy resin composition that provides a hardened material excellent in heat resistance and water resistance, a prepreg formed by impregnating a fiber substrate, a resin sheet, a metal-clad laminate, a printed wiring board, and a semiconductor. Device.

Epoxy resin compositions are widely used in electrical / electronic parts, structural materials, adhesives, coatings, etc. due to their excellent electrical properties, heat resistance, adhesion, and moisture resistance (water resistance), etc. in.

However, in recent years, in the electrical / electronic field, with its development, moisture resistance, adhesion, dielectric properties, and the like (inorganic or organic fillers) have been demanded, including high purity of resin compositions. Various properties such as high filling and low viscosity, and improved reactivity for shortening the molding cycle are further improved. In addition, as structural materials, materials that are lightweight and excellent in mechanical properties are required for aerospace materials, entertainment / sports equipment applications, and the like. Especially in the field of semiconductor sealing and the substrate (the substrate itself or its peripheral materials), the required characteristics are increasing year by year, for example, the Tg of peripheral materials is required to be increased due to the increase in the driving temperature of the semiconductor.

In general, when the Tg of the epoxy resin is increased, the water absorption rate increases (Non-Patent Document 1). This is due to the increase in crosslinking density. However, in the case where semiconductor Tg, which requires low moisture absorption, is required to have a high Tg, development of a resin having these opposite characteristics is an urgent task.

On the other hand, Patent Document 1 discloses a phenol-based novolak resin having a biphenyl skeleton and a phenol-based novolak-type epoxy resin obtained by epoxidizing the phenol-based novolak resin, and it is described as useful for the use of a semiconductor sealant. Sex.

However, the present epoxy resin is a combination with a phenol resin, and has both high heat resistance and flame resistance, but has a high water absorption rate, and has a problem when it is used for electronic materials that require very high reliability.

In addition, there is no description about the characteristics of the composition containing these epoxy resins and amine-based hardeners, and there is no description about the usefulness of printed wiring board applications.

Patent Document 1: Japanese Patent Application Publication No. 2013-43958

Non-Patent Document 1: Koshiro Ichiro, "Relationship between Chemical Structure and Properties of Epoxy Resin", DIC Technical Review No. 7, Japan, 2001, p. 7

The present invention has been made as a result of research to solve such problems, and an object thereof is to provide an epoxy resin composition and a prepreg, a resin sheet, a metal-clad laminated board, a printed wiring board, and a semiconductor device using the same. The cured product of the epoxy resin composition has high heat resistance, water absorption, and low dielectric constant.

The present inventors have made intensive studies in order to solve the above problems, and as a result, have completed the present invention.

That is, the present invention provides: (1) an epoxy resin composition comprising an epoxy resin and an amine-based hardener represented by the following general formula (1) as essential components,

(In the formula, the ratio of (a) (b) is (a) / (b) = 1 ~ 3; G is epoxy group; n is the repeating number, 0 ~ 5); (2) a prepreg , Which is obtained by impregnating the fibrous substrate with the epoxy resin composition according to the above (1); (3) the prepreg according to the above (2), wherein the fibrous substrate is a glass fiber substrate; (4) The prepreg according to the above (3), wherein the glass fiber substrate comprises at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass; (5) ) A metal-clad laminated board having metal foil layered on at least one area of the prepreg according to any one of (2) to (4) above; (6) A resin sheet formed by forming an insulating layer composed of the epoxy resin composition described in the above (1) on a film or a metal foil; (7) a printed wiring board comprising the above (5) The metal-clad laminated board according to (5) is used for an inner-layer circuit board; (8) A printed wiring board, which is the prepreg according to any one of (2) to (4) above or the above (6) The resin sheet according to (6) is hardened; (9) A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to (7) or (8) above.

The epoxy resin composition of the present invention provides a hardened material capable of achieving high heat resistance and water resistance at the same time. Therefore, the epoxy resin composition is extremely useful as a laminated board such as a printed wiring board or a build-up substrate.

According to the present invention, an epoxy resin composition and a prepreg, a resin sheet, a metal-clad laminated board, a printed wiring board, and a semiconductor device using the same can be provided. The hardened product of the epoxy resin composition has high heat resistance and Water absorption and low dielectric constant.

Figure 1 shows the heat resistance and water absorption characteristics of a cured product of an epoxy resin composition. Relationship chart.

Hereinafter, the epoxy resin composition of this invention is demonstrated.

The epoxy resin composition of the present invention includes an compound represented by the following formula (1) as an epoxy resin (hereinafter, referred to as "epoxy resin of formula (1)") and an amine hardener as essential components.

(In the formula, the ratio of (a) (b) is (a) / (b) = 1 ~ 3; G represents epoxypropyl group; n is the repeating number, 0 ~ 5).

The epoxy resin of the formula (1) used in the present invention can use Japanese Patent Application Laid-Open No. 2011-252037, Japanese Patent Application Laid-Open No. 2008-156553, Japanese Patent Application Laid-Open No. 2013-043958, International Publications WO2012 / 053522, WO2007 / Synthesis is performed by the method described in 007827, but any method may be used as long as it has the structure of the formula (1).

Among them, in the present invention, in particular, the ratio (polyfunctionalization ratio) of the above formula (a) to the above formula (b) is (a) / (b) = 1 to 3. When the structure of (a) is large, heat resistance is improved, but not only the water absorption characteristics are deteriorated, but also brittle and hardened. Therefore, those having a polyfunctionality within the above range are used.

The softening point (ring and ball method) of the epoxy resin used is preferably 50 to 150 ° C, more preferably 52 to 100 ° C, and even more preferably 52 to 95 ° C. If it is 50 ° C or lower, there is a case where the stickiness is strong, the operation is difficult, and a problem occurs in terms of productivity. In addition, when the temperature is 150 ° C or higher, the temperature is close to the molding temperature, and the fluidity during molding may not be secured, which is not preferable.

The epoxy equivalent of the epoxy resin used is preferably 180 to 350 g / eq. Especially preferred is 190 ~ 300g / eq. When the epoxy equivalent is less than 180 g / eq., There are too many functional groups, and therefore the water absorption of the hardened product after hardening becomes high, and it becomes easy to become brittle. When the epoxy equivalent exceeds 350 g / eq., It is considered that the softening point becomes very large, or the epoxidation does not proceed, and the amount of chlorine becomes very large, which is not preferable.

The chlorine content of the epoxy resin used in the present invention is preferably 200 to 1500 ppm, and more preferably 200 to 900 ppm, based on the total chlorine (hydrolysis method). According to JPCA standards, it is expected that the amount of chlorine will not exceed 900 ppm even if it is an epoxy monomer. Furthermore, if the amount of chlorine is large, the excess chlorine may affect the electrical reliability, which is not preferable. In the case where the amount of chlorine is less than 200 ppm, an excessive purification step is required, and a problem arises in terms of productivity, which is not preferable.

Furthermore, the melt viscosity of the epoxy resin used in the present invention at 150 ° C. is preferably 0.05 to 5 Pa. s, particularly preferably 0.05 ~ 2.0Pa. s. If the melt viscosity is higher than 5Pa. s, there are cases where fluidity causes problems, and fluidity or embedding when pressure occurs. The melt viscosity is less than 0.05Pa. In the case of s, the molecular weight is too small, and thus the heat resistance may be insufficient.

The ratio of (a) and (b) in the above formula is (a) / (b) = 1 ~ 3. That is, it is characterized by having more than half of a glycidyl ether having a resorcinol structure. This ratio is important for precipitation of crystals and improvement of heat resistance, and it is preferable that (a) / (b) exceeds 1. Also, with (a) / (b) being 3 In the following, the amount of glycidyl ether having a resorcinol structure is limited, thereby improving water absorption and toughness.

In the above formula, n is a repeating unit and is 0 to 5. With n not exceeding 5, the smoothness or fluidity of the prepreg or resin sheet is controlled. In the case where n exceeds 5, not only a problem arises in flowability, but also a problem in solubility in a solvent.

The solubility of the epoxy resin used in the present invention in a solvent becomes important. For example, when a biphenylaralkyl-type epoxy resin having the same skeleton is used in combination, these resins also require solubility in solvents such as methyl ethyl ketone, toluene, and propylene glycol monomethyl ether.

In the present invention, the solubility in methyl ethyl ketone is important, and it is required that crystals do not precipitate at 5 ° C. or room temperature for 2 months or more. It is also related to the ratio of (a) / (b), and if the value of (a) is large, the crystals will be easily precipitated. Therefore, it is important that (a) / (b) is 1 or more.

The epoxy resin composition of the present invention contains an amine hardener as an essential component. Examples of the usable amine hardener include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfonium, isophoronediamine, naphthalenediamine, Aniline and substituted biphenyls (4,4'-bis (chloromethyl) -1,1'-biphenyl and 4,4'-bis (methoxymethyl) -1,1'-biphenyl, etc.) Or substituted polycondensation of phenyls (1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, 1,4-bis (hydroxymethyl) benzene, etc.) The obtained aniline resin and the like are not limited thereto.

A particularly preferable amine-based hardener is a difunctional or more functional amine compound, and a resin having a structure represented by the following formula is preferred.

(In the formula, n is a repeating number, and is 1 to 10).

The amine hardener used in the present invention has the shape of a crystal or a resin, respectively.

In the case of crystallization, the melting point is preferably 35 to 200 ° C, and particularly preferably 40 to 185 ° C. In the case of melting point, unlike the softening point, it is also related to the solubility in other resins, so it does not have to be a temperature below the molding temperature like the resin.

In the case of a resin, a softening point (ring and ball method) of 50 ° C to 150 ° C is preferred, and 50 to 100 ° C is particularly preferred. In the case of resin, if the softening point is below 50 ° C, there are problems with stickiness, so it is not good. When the softening point exceeds 150 ° C, there may be problems with fluidity during molding, and it cannot be completely molded. Solvent cannot be removed.

The functional group equivalent of the amine compound is preferably 60 to 600 g / eq. (Measurement by potentiometric titration). When the active hydrogen equivalent is 60 or less, the hardened | cured material may have a problem in water absorption or toughness. When the active hydrogen equivalent exceeds 600, it may be difficult to maintain heat resistance.

In the epoxy resin composition of the present invention, regarding the amount of amine hardener used, It is preferably 0.2 to 0.6 equivalents based on the amine equivalents of the epoxy compound relative to 1 equivalent of the epoxy group. Especially preferred is 0.3 to 0.55 equivalents. When it is less than 0.2 equivalents with respect to 1 equivalent of epoxy groups, and when it exceeds 0.6 equivalents, it may be incompletely hardened and good hardened physical properties may not be obtained, which is not preferable.

The epoxy resin composition of the present invention may contain a hardening accelerator. Specific examples of usable hardening accelerators include formic acid, acetic acid, lactic acid, glycolic acid, n-butyric acid, isobutyric acid, propionic acid, hexanoic acid, caprylic acid, n-heptanoic acid, monochloroacetic acid, and dichloroacetic acid. , Trichloroacetic acid, thioglycolic acid, phenol, m-cresol, p-chlorophenol, p-nitrophenol, 2,4-dinitrophenol, o-aminophenol, p-aminophenol, 2,4,5- Trichlorophenol, resorcinol, hydroquinone, catechol, resorcinol, benzoic acid, p-toluic acid, p-aminobenzoic acid, p-chlorobenzoic acid, 2,4-dichlorobenzoic acid , Salicylic acid, phthalic acid, isophthalic acid, terephthalic acid, malic acid, oxalic acid, succinic acid, malonic acid, fumaric acid, maleic acid, tartaric acid, citric acid and other acids; monoethanolamine, Diethanolamine, triethanolamine and other amines; thiophenol, 2-mercaptoethanol, sulfur-containing; 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole and other imidazoles; 2- Tertiary amines such as (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5,4,0] undecene-7; phosphines such as triphenylphosphine; metals such as stannous octoate Compounds etc. The hardening accelerator is used in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

The epoxy resin composition of the present invention may be used in combination with other epoxy resins. Specific examples of other epoxy resins that can be used in combination with the epoxy resin of formula (1) include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenol (Phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl Aldehyde, benzaldehyde, alkyl Substituted polycondensates of benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc .; the above phenols and various diene compounds (dicyclopentadiene, terpenes) , Vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Polymers of the above; polycondensates of the above phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); the above phenols and aromatic dimethanols Polycondensates of (xylylene, biphenyldimethanol, etc.); polycondensates of the above phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethyl biphenyl, etc.) A polycondensate of the above phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.); Glycidyl ether epoxy resin, alicyclic epoxy resin, propylene oxide epoxy resin, propylene oxide epoxy resin, etc. Department of epoxy resin, etc. The epoxy resins typically used as long as it is not limited to such. These can be used alone or in combination of two or more.

When the epoxy resin composition of the present invention is blended, a conventionally known hardener can be used in combination. Examples of other curing agents that can be used in combination include acid anhydride compounds, amidine compounds, phenol compounds, and carboxylic acid compounds. Specific examples of usable hardeners include ammonium compounds such as polyamine resins synthesized from dicyandiamine, a dimer of linolenic acid, and ethylenediamine; phthalic anhydride, Trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl dianhydride, hexahydrophthalic anhydride, methyl Acid anhydride compounds such as hexahydrophthalic anhydride; bisphenol A, bisphenol F, bisphenol S, bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3, 3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris (4-hydroxybenzene Group) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane or phenols (phenol, alkyl-substituted phenol, Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, furfural The polycondensate is novolac resin, or the reaction product of phenol or cresol with phenylene dimethylol, dimethoxymethyl or halogenated methyl, or phenol or cresol with bischloromethyl Reactant of biphenyl, bismethoxymethylbiphenyl or bismethylolbiphenyl, or reactant of phenol with benzenediisopropanol, benzenediisopropanol dimethyl ether or phenylbis (chloroisopropane) That is, phenol aralkyl resins and modified products thereof, or halogenated bisphenols such as tetrabromobisphenol A, or phenolic compounds such as polycondensates of terpenes and phenols; imidazole, boron trifluoride-amine complex Substances, guanidine derivatives, and the like, but are not limited to these. These can be used alone or in combination of two or more.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a component imparting flame retardancy. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresol phosphate, tris (xylyl) phosphate, cresol phosphate diphenyl, and cresol phosphate 2,6 -Bis (xylyl) ester, 1,3-phenylene bis (bis (xylyl) phosphate), 1,4-phenylene bis (bis (xylyl) phosphate), 4,4 Phosphate-based compounds such as' -biphenyl (bis (xylyl) phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5- Dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and other phosphines; phosphorus-containing epoxy compounds and red obtained by reacting epoxy resin with the above-mentioned phosphine active hydrogen Phosphorus and the like are preferably phosphates, phosphines, or phosphorus-containing epoxy compounds, and particularly preferably 1,3-phenylenebis (bis (xylyl) phosphate), 1,4-phenylenebis ( Bis (xylyl) phosphate), 4,4'-biphenyl (bis (xylyl) phosphate) or phosphorus-containing epoxy compounds.

However, based on environmental concerns and concerns about electrical characteristics, the use amount of the phosphate ester compound as described above is preferably phosphate ester compound / epoxy resin ≦ 0.1 (weight ratio). More preferably 0.05 the following. It is particularly preferred not to add a phosphorus-based compound in addition to adding it as a hardening accelerator.

The epoxy resin composition of the present invention may contain an inorganic filler. Examples of the inorganic filler include fused silica, crystalline silica, alumina, calcium carbonate, calcium silicate, barium sulfate, talc, clay, magnesium oxide, aluminum oxide, beryllium oxide, iron oxide, and titanium oxide. , Aluminum nitride, silicon nitride, boron nitride, mica, glass, quartz, mica, etc. In order to further impart a flame retardant effect, metal hydroxides such as magnesium hydroxide and aluminum hydroxide are also preferably used. But it is not limited to these. Moreover, you may use it, mixing 2 or more types. Among these inorganic fillers, silicon dioxide such as fused silicon dioxide or crystalline silicon dioxide is low in cost and good in electrical reliability, so it is preferable.

In the epoxy resin composition of the present invention, the amount of the inorganic filler used is within a proportion, usually 5 to 70% by weight, preferably 10 to 60% by weight, and more preferably 15 to 60% by weight. % Range. If the amount of the inorganic filler used is too small, the linear expansion becomes high and warpage becomes a problem, or as the substrate becomes thinner, there is no possibility that the rigidity will cause problems in the stroke. In addition, if the amount of the inorganic filler used is too large, problems such as loss of homogeneity due to precipitation of the filler, deterioration of the embedding property of the substrate, and deterioration of the adhesion with the metal may occur. In the case of a substrate, there is a high possibility of adverse effects on electrical characteristics such as peeling or breaking voltage.

In addition, the shape, particle size, and the like of the inorganic filler are not particularly limited, but are usually those having a particle size of 0.01 to 50 μm, preferably 0.1 to 15 μm.

In the epoxy resin composition of the present invention, a mold release agent may be blended in order to improve the mold release from the mold during molding. As the release agent, any of the conventionally known ones can be used, and examples thereof include ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid, and metal salts thereof, oxidized polyethylene, non- Polyolefin waxes such as oxidized polyethylene. These can be used alone You can also use 2 or more types together. The blending amount of these release agents is preferably 0.5 to 3% by weight relative to all organic components. If it is excessively less than the above range, the mold release from the mold may be deteriorated, and if it is excessively more than the above range, the adhesion to the substrate and the like may be deteriorated.

A coupling agent may be blended in the epoxy resin composition of the present invention in order to improve the adhesion between the inorganic filler and the resin component. As the coupling agent, any of the conventionally known ones can be used, and examples thereof include vinylalkoxysilane, epoxyalkyloxysilane, styrylalkoxysilane, methacryloxyalkoxysilane Various alkoxy silane compounds such as propylene alkoxy alkoxy silane, amino alkoxy silane, mercapto alkoxy silane, isocyanate alkoxy silane, titanium alkoxy compounds, aluminum chelate compounds, etc. These can be used alone or in combination of two or more. Regarding the method of adding the coupling agent, the surface of the inorganic filler may be treated with the coupling agent in advance, and then mixed with the resin, or the inorganic filler may be mixed after the coupling agent is mixed with the resin.

An organic solvent can be added to the epoxy resin composition of the present invention to form a varnish-like composition (hereinafter, simply referred to as a varnish). Examples of the solvent to be used include γ-butyrolactones, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and N, N -Ammonium solvents such as dimethylimidazolidone; fluorenes such as tetramethylene hydrazone; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoethyl Ether solvents such as acid esters and propylene glycol monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; aromatic solvents such as toluene and xylene. The solvent is used in the range of usually 10 to 80% by weight, preferably 20 to 70% by weight of the solid content concentration in the obtained varnish, except for the solvent.

Further, a known additive may be blended into the epoxy resin composition of the present invention as necessary. Specific examples of the usable additives include polybutadiene and modified products thereof, and propylene Modified copolymers of polyacrylonitrile, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide-based compound, cyanate-based compound, polysiloxane gel, polysiloxane Oil, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

The resin sheet of the present invention will be described.

The resin sheet using the epoxy resin composition of the present invention is a thickness after drying the varnish by various coating methods such as a gravure coating method, screen printing, metal mask method, and spin coating method known per se. It can be obtained after being coated on a flat support with a specific thickness, for example, 5 to 100 μm, and then dried. However, which coating method is used depends on the type, shape, size, film thickness, and support of the support. The heat resistance of the body is appropriately selected.

Examples of the planar support include polyimide, polyimide, imine, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyether ketone, and polyether fluorene. Films made of various polymers such as imine, polyetheretherketone, polyketone, polyethylene, polypropylene, Teflon (registered trademark) and / or copolymers thereof, or metal foils such as copper foil.

After coating and drying, a sheet-like composition (the resin sheet of the present invention) can be obtained, but the sheet-like cured product can also be produced by further heating the resin sheet. It is also possible to perform both the solvent drying and hardening steps by one heating.

Regarding the epoxy resin composition of the present invention, both sides or one side of the support may be coated by the method described above and heated to form a hardened layer on both or one side of the support. Moreover, a laminated body can also be produced by bonding an adherend before hardening and hardening it.

In addition, the resin sheet of the present invention can be used as an adhesive sheet by being peeled from a support, or can be brought into contact with an adherend, and if necessary, pressure and heat are applied to harden and adhere together.

The prepreg of the present invention will be described.

The prepreg system of the present invention is obtained by impregnating the aforementioned epoxy resin composition of the present invention with a fiber substrate. Thereby, a prepreg having excellent heat resistance, low expansion, and flame retardancy can be obtained. Examples of the fiber substrate include glass fiber substrates such as glass woven fabrics, glass nonwoven fabrics, and cellophane; woven fabrics composed of synthetic fibers such as paper, polyamide, polyester, aromatic polyester, and fluororesin. Or non-woven fabrics; woven fabrics, non-woven fabrics, mats, etc. composed of metal fibers, carbon fibers, mineral fibers, etc. These substrates can be used alone or in combination. Among these, a glass fiber substrate is preferable. This can further improve the rigidity and dimensional stability of the prepreg.

The glass fiber substrate preferably contains at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass.

The method of impregnating the above-mentioned fibrous substrate with the epoxy resin composition of the present invention includes, for example, a method of immersing the substrate in a resin varnish, a method of coating with various coating machines, and a spraying method using a sprayer. Methods, etc. Among these, the method of immersing a base material in a resin varnish is preferable. This can improve the impregnation of the resin composition with the substrate. When the substrate is immersed in a resin varnish, an ordinary impregnation coating equipment can be used.

For example, after impregnating the epoxy resin composition of the present invention directly or in the form of a varnish obtained by dissolving or dispersing it in a solvent, it is impregnated into a substrate such as glass cloth, and then in a drying furnace at a temperature of usually 80 to 200 ° C (wherein, When a solvent is used, the prepreg is obtained by drying at a temperature higher than the temperature at which the solvent can be volatilized) for 2 to 30 minutes, preferably 2 to 15 minutes.

The metal-clad laminate of the present invention will be described.

The laminated board used in the present invention is obtained by heating and pressing the prepreg of the present invention. Thereby, a metal-clad laminate having excellent heat resistance, low expansion, and flame retardancy can be obtained. In the case of a single prepreg, metal foil is superposed on the upper and lower sides or on one side. It is also possible to combine 2 tablets with The above prepreg was laminated. When two or more prepregs are laminated, metal foils or films are superposed on the upper and lower sides or on one side of the outermost prepregs. Next, a metal cladding laminate can be obtained by heating and pressing the prepreg and the metal foil. The temperature for heating is not particularly limited, but is preferably 120 to 220 ° C, and particularly preferably 150 to 200 ° C. The pressure for pressurizing is not particularly limited, but is preferably 1.5 to 5 MPa, and particularly preferably 2 to 4 MPa. Further, if necessary, post-curing may be performed in a high-temperature tank or the like at a temperature of 150 to 300 ° C.

The printed wiring board of the present invention will be described.

The printed wiring board of the present invention uses the metal-clad laminated board of the present invention as the inner-layer circuit board. Circuit formation is performed on one or both sides of the metal-clad laminate. According to circumstances, through holes can be formed by drilling and laser processing, and electrical connection on both sides can be achieved by plating.

A commercially available resin sheet of the present invention or the above-mentioned prepreg of the present invention can be superimposed on the above-mentioned inner-layer circuit board and heated and press-molded to obtain a multilayer printed wiring board.

Specifically, the insulating layer side of the resin sheet and the inner circuit board are overlapped, and vacuum heating and pressure molding is performed using a vacuum pressure type bonding device or the like, and then the insulating layer may be formed by a hot air drying device or the like. Obtained by heat hardening.

Here, the conditions for performing the heat and pressure molding are not particularly limited. For example, the conditions can be implemented at a temperature of 60 to 160 ° C and a pressure of 0.2 to 3 MPa. The conditions for heat curing are not particularly limited. For example, they can be carried out at a temperature of 140 to 240 ° C for 30 to 120 minutes.

Alternatively, it can also be obtained by superimposing the prepreg of the present invention on the inner-layer circuit board, and heating and pressing it using a flat plate press or the like. Here, the conditions for performing the heat and pressure molding are not particularly limited, and for example, the conditions can be implemented at a temperature of 140 to 240 ° C and a pressure of 1 to 4 MPa. In such a heating and press molding using a flat plate pressing device or the like, Heating and hardening of the insulating layer are performed while forming.

In addition, the method for manufacturing a multilayer printed wiring board of the present invention includes the steps of: continuously stacking the above-mentioned resin sheet or the prepreg of the present invention on a surface of the inner-layer circuit substrate on which the inner-layer circuit pattern is formed, and borrowing A step of forming a conductor circuit layer by a semi-additive method.

Regarding the hardening of the insulating layer formed of the resin sheet or the prepreg of the present invention, in order to facilitate the subsequent laser irradiation and the removal of resin residues, and to improve the desmear property, it is pre-set In the case of a semi-hardened state. In addition, the first insulating layer is heated at a temperature lower than the normal heating temperature, thereby hardening (semi-hardening) a part of the insulating layer, and then forming one or even a plurality of insulating layers to insulate the semi-hardened insulation. The layer is heated and hardened again to the extent that it is practically problem-free, thereby improving the adhesion between the insulating layers and between the insulating layer and the circuit. The semi-hardened temperature in this case is preferably 80 ° C to 200 ° C, and more preferably 100 ° C to 180 ° C. In the subsequent steps, the laser is irradiated to form an opening in the insulating layer. However, before this, the substrate must be peeled off. Regarding peeling of the substrate, there is no particular problem even if the peeling is performed at any time after the insulating layer is formed, before the heat curing, or after the heat curing.

In addition, the inner-layer circuit board used in obtaining the multilayer printed wiring board may be formed by, for example, forming specific conductor circuits on both sides of the copper-clad laminated board by etching or the like, and subjecting the conductor circuit portion to blackening treatment. By.

The resin residues and the like after laser irradiation are preferably removed using an oxidant such as permanganate and dichromate. In addition, the surface of the smooth insulating layer can be roughened at the same time, and the adhesion of the conductive wiring circuit formed by metal plating can be improved later.

Next, an outer layer circuit is formed. The formation method of the outer layer circuit is to realize the connection between the insulating resin layers by metal plating, and to form the outer layer circuit pattern by etching. Available with When a resin sheet or a prepreg is used, the same procedure is performed to obtain a multilayer printed wiring board.

When a resin sheet or a prepreg having a metal foil is used, the circuit is formed by etching to prevent the metal foil from being used as a conductor circuit. In this case, if an insulating resin sheet with a base material using a thick copper foil is used, it becomes difficult to fine-pitch in subsequent circuit pattern formation. Therefore, an extremely thin copper foil of 1 to 5 μm is also used, or A case where a copper foil having a thickness of 12 to 18 μm is thinned to a half etching of 1 to 5 μm by etching is performed.

It is also possible to further laminate an insulating layer and perform the same circuit formation as described above, but for the design of a multilayer printed wiring board, after forming the circuit at the outermost layer, a solder resist layer is formed. The method for forming the solder resist layer is not particularly limited, for example, it is formed by a method of laminating (laminating) a dry film type solder resist layer, and exposing and developing the solder resist layer; or by A method in which a liquid resist is printed and exposed and developed. When the obtained multilayer printed wiring board is used in a semiconductor device, a connection electrode portion is provided for mounting a semiconductor element. The connection electrode portion may be appropriately covered with a metal film such as gold plating, nickel plating, and solder plating. A multilayer printed wiring board can be manufactured by the above method.

Next, a semiconductor device of the present invention will be described.

A semiconductor element having solder bumps is mounted on the multilayer printed wiring board obtained in the above, and connection with the multilayer printed wiring board is achieved through the solder bumps. Then, a liquid sealing resin is filled between the multilayer printed wiring board and the semiconductor element to form a semiconductor device. The solder bump is preferably made of an alloy made of tin, lead, silver, copper, bismuth, or the like.

Regarding the method of connecting the semiconductor element to the multilayer printed wiring board, an IR reflow device is used after aligning the position of the electrode portion for connection on the substrate with the solder bump of the semiconductor element using a flip-chip bonding machine or the like. , Hot plate, other heating device to heat the welding bump to Above the melting point, the multilayer printed wiring board and the solder bump are fusion-bonded to perform connection. Furthermore, in order to improve connection reliability, a metal layer having a relatively low melting point, such as a solder paste, may be formed in advance on the connection electrode portion on the multilayer printed wiring board. Before this bonding step, a soldering flux and / or a surface layer of a connection electrode portion on a multilayer printed wiring board may be coated with a flux, thereby improving connection reliability.

As the substrate, it is used for a mother board, a mesh substrate, a package substrate, and the like, and is used as a substrate. It is especially useful as a package substrate and a thin-layer substrate for a single-sided sealing material. In the case of using as a semiconductor sealing material, examples of the semiconductor device obtained by the blending include: DIP (Dual inline package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Scale Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP ( Thin Quad Flat Package).

Examples

The synthesis examples and examples are listed below to further specifically describe the features of the present invention. The materials, processing contents, processing procedures, and the like shown below can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the specific examples shown below.

Here, the measurement conditions of each physical property value are as follows.

． Epoxy equivalent

Measured by the method described in JIS K-7236, the unit is g / eq.

． Softening Point

Measured by the method according to JIS K-7234, the unit is ° C.

． Modulus of Elasticity (DMA)

Dynamic viscoelasticity measuring device: TA-instruments, DMA-2980

Measuring temperature range: -30 ~ 280 ℃

Heating rate: 2 ℃ / min

Test piece size: use cutting 5mm × 50mm

Tg: Set the peak point of Tan-δ in DMA measurement as Tg

． Water absorption

Weight increase rate (%) after boiling a disc-shaped test piece with a diameter of 5 cm and a thickness of 4 mm in water at 100 ° C for 72 hours

Synthesis Example 1

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a phenol resin ((a) / (b) = 1.3n = 1.5 hydroxyl group) represented by the following formula manufactured according to WO2007 / 007827 was added while purging with nitrogen. The equivalent weight is 134 g / eq. (Softening point: 93 ° C) 134 parts, 450 parts of epichlorohydrin, and 54 parts of methanol, and they are dissolved under stirring, and the temperature is raised to 70 ° C. Then, 42.5 parts of flake-shaped sodium hydroxide was added in portions over 90 minutes, and then reacted at 70 ° C. for 1 hour. After completion of the reaction, washing with water and removal of salts were performed, and the obtained organic layer was subjected to a rotary evaporator under reduced pressure to remove excess solvents such as epichlorohydrin by distillation. Add 500 parts of methyl isobutyl ketone to the residue and dissolve, add 17 parts of 30% by weight aqueous sodium hydroxide solution under stirring, and perform reaction for 1 hour, then wash with water until the washing water of the oil layer becomes neutral, and use a spin From the obtained solution, methyl isobutyl ketone and the like were distilled off under reduced pressure in an evaporator, thereby obtaining 195 parts of epoxy resin (EP1) of formula (1). The epoxy equivalent of the obtained epoxy resin was 211 g / eq., And the softening point was 71 ° C. The 150 ° C melt viscosity (ICI melt viscosity cone # 1) is 0.34Pa. s.

Example 1

For the epoxy resin (EP1) obtained in Synthesis Example 1, A-1 was blended with respect to 1 mol equivalent of epoxy equivalent (amine equivalent 198 g / eq, active hydrogen equivalent 97.5 g / eq, and softening point 55 ° C). 0.5 equivalent was used as a hardener, and salicylic acid was mixed as a catalyst at a ratio of 1 part by weight to 100 parts by weight of the epoxy resin, and the mixture was uniformly mixed and kneaded using a mixing roller to obtain an epoxy resin composition. . This epoxy resin composition was pulverized with a stirrer, and further ingotized with a tablet press. This ingot-formed epoxy resin composition was injection-molded (175 ° C × 60 seconds), and then demolded at 160 ° C × 2 hours + 180 ° C × 6 hours to obtain a test piece for evaluation. . The evaluation results are shown in Table 1.

The details of the epoxy resin used in the evaluation are shown in Table 2 below.

Comparative Examples 1 to 7

In Example 1, for the epoxy resin (EP1) obtained in Synthesis Example 1, and various epoxy resins, an equivalent equivalent of A-1 or HA-1 (a phenolic novolac manufactured by Meiwa Chemical Industry Co., Ltd.) was used. Resin) was used as a hardener, and triphenylphosphine (TPP) or salicylic acid was used as a catalyst, and a test piece for evaluation was obtained by the same formulation and method as in Example 1. The evaluation results are shown in Table 1.

According to Table 1, it is confirmed that when Example 1 is compared with Comparative Example 3, hardening with good heat resistance and water absorption characteristics can be specifically formed by using an amine-based hardener compared with the case where a phenol resin is used as the hardener. Thing.

The hardened physical properties obtained in Table 1 are shown in FIG. 1 with heat resistance (Tg) as the horizontal axis and water absorption characteristics (%) as the vertical axis.

From FIG. 1, it was confirmed that the hardened materials of Comparative Examples 1 to 3 and Comparative Examples 4 to 7 had a correlation between an increase in water absorption as Tg increased. On the other hand, it was confirmed that the hardened | cured material using the epoxy resin and amine hardening | curing agent of Formula (1) has a high water resistance, but low water absorption, and it is a specific combination different from the said correlation.

The present invention has been described in detail with reference to specific aspects, but practitioners understand that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Furthermore, this application is based on a Japanese patent application filed on August 1, 2014 (Japanese Patent Application No. 2014-157629), and the entirety thereof is incorporated by reference. Also, all references cited herein are incorporated herein in their entirety.

[Industrial availability]

The epoxy resin composition of the present invention provides a cured product which can achieve both high heat resistance and water resistance, and is therefore a very useful material for producing a laminated board such as a printed wiring board or a build-up substrate.

Claims (9)

An epoxy resin composition comprising an epoxy resin and an amine hardener represented by the following general formula (1) as essential components, the amine hardener is a difunctional or more functional amine compound, and the functional group equivalent is 60 g / eq. . ~ 600g / eq., (In the formula, the ratio of (a) (b) is (a) / (b) = 1 ~ 3; G represents epoxypropyl group; n is the repeating number, 0 ~ 5). A prepreg is obtained by impregnating an epoxy resin composition in the scope of patent application No. 1 with a fiber substrate. For example, the prepreg of item 2 of the patent application scope, wherein the fiber substrate is a glass fiber substrate. For example, the prepreg according to item 3 of the patent application scope, wherein the glass fiber substrate contains at least one selected from the group consisting of T glass, S glass, E glass, NE glass, and quartz glass. A metal-clad laminated board having metal foil layered on at least one area of the prepreg according to any one of claims 2 to 4. A resin sheet is formed by forming an insulating layer composed of an epoxy resin composition as claimed in claim 1 on a film or a metal foil. A printed wiring board is formed by using a metal-clad laminated board with a scope of patent application No. 5 for an inner-layer circuit board. A printed wiring board is formed by hardening a prepreg according to any one of claims 2 to 4 or a resin sheet according to claim 6. A semiconductor device is formed by mounting a semiconductor element on a printed wiring board with a patent application scope of item 7 or 8.